Diacetylenic materials for sensing applications

ABSTRACT

Diacetylenic materials for the colorimetric detection of an analyte or exposure to certain environmental factors are disclosed as well as the polymerization reaction products of these diacetylenic compounds.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.11/177,643, filed Jul. 8, 2005, which is a division of U.S. patentapplication Ser. No. 10/325,276, filed Dec. 19, 2002, now U.S. Pat. No.6,963,007.

FIELD OF THE INVENTION

This invention relates to diacetylenic materials for the colorimetricdetection of an analyte or exposure to certain environmental factors. Inaddition, the invention relates to the polymerization reaction productsof at least one of the diacetylenic compounds disclosed herein.

BACKGROUND OF THE INVENTION

Various circumstances require that exposure to certain environmentalfactors, such as heat and ultraviolet (UV) light be monitored andrecorded. For example, the need to know whether a product has beenexposed either to an undesirable time-temperature history, which resultsin substantial degradation, or to a correct time-temperature historyrequired during processing is frequently required. This applies, forexample, to frozen foods, pharmaceuticals or photographic films that maybe exposed to undesirable high temperatures for significant time periodsduring storage and distribution. Additionally, exposure to theultraviolet radiation of sunlight can cause rapid aging and hardening ofthe skin and can cause DNA damage, which can lead to skin cancer orother cellular proliferative diseases.

Diacetylenes are typically colorless and undergo additionpolymerization, either thermally or by actinic radiation. As thepolymerization proceeds, these compounds undergo a contrasting colorchange to blue or purple. Utilization of this class of compounds isknown for use as time-temperature history indicators, thermochromicindicating materials and as radiation-dosage indicators.

Efforts continue, however, to make sensing devices employingdiacetylenes more accurate, more tailored to a given application, lesscomplex and more available to non-technical personnel in a wide varietyof environments. Devices, which can be conveniently transported and usedindividually for a particular application then discarded, areparticularly desirable.

SUMMARY OF THE INVENTION

The present invention relates to compounds of the formula

-   -   where R¹ is

-   -   R² is        -   alkylamino,

-   -   R³, R⁸, R¹³, R²⁴, R³¹ and R³³ are independently alkyl; R⁴, R⁵,        R⁷, R¹⁴, R¹⁶, R¹⁹, R²⁰, R²², R²⁵, and R³² are independently        alkylene; R⁶, R¹⁵, R¹⁸, and R²⁶ are independently alkylene,        alkenylene, or arylene; R⁹ is alkylene or —NR³⁴—; R¹⁰, R¹², R²⁷,        and R²⁹ are independently alkylene or alkylene-arylene; R¹¹ and        R²⁸ are independently alkynyl; R¹⁷ is 2,5-dioxo-1-pyrrolidinyl;        R²¹ is alkylamino or alkyl; R²³ is arylene; R³⁰ is alkylene or        —NR³⁶—; R³⁴, and R³⁶ are independently H or C₁-C₄ alkyl; p is        1-5; and n is 1-20; and where R¹ and R² are not the same.

Also provided is a method for the detection of electromagnetic radiationin the ultraviolet range of the electromagnetic spectrum comprisingcontacting at least one compound described above with electromagneticradiation in the ultraviolet range of the electromagnetic spectrum andobserving a color change.

Also provided is a polymerized composition including the polymerizationreaction product of at least one compound described above.

Also provided is a method for the detection of thermal radiationincluding contacting a polymerized composition described above withthermal radiation and observing a color change.

The above summary of the present invention is not intended to describeeach disclosed embodiment or every implementation of the presentinvention. The detailed description that follows more particularlyexemplifies these embodiments.

DETAILED DESCRIPTION

The present invention provides for diacetylenic materials. Inparticular, the present invention is directed to diacetylenic materialsfor the colorimetric detection of an analyte or exposure to certainenvironmental factors. While the present invention is not so limited, anappreciation of various aspects of the invention will be gained througha discussion of the examples provided below.

All numbers are herein assumed to be modified by the term “about.”

The recitation of numerical ranges by endpoints includes all numberssubsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3,3.80, 4, and 5).

For the following defined terms, these definitions shall be applied,unless a different definition is given in the claims or elsewhere inthis specification.

As used herein, the term “alkyl” refers to a straight or branched chainor cyclic monovalent hydrocarbon radical having a specified number ofcarbon atoms. Alkyl groups include those with one to twenty carbonatoms. Examples of “alkyl” as used herein include, but are not limitedto, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, and isopropyl,and the like. It is to be understood that where cyclic moieties areintended, at least three carbons in said alkyl must be present. Suchcyclic moieties include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyland cycloheptyl.

As used herein, the term “alkylene” refers to a straight or branchedchain or cyclic divalent hydrocarbon radical having a specified numberof carbon atoms. Alkylene groups include those with one to fourteencarbon atoms. Examples of “alkylene” as used herein include, but are notlimited to, methylene, ethylene, trimethylene, tetramethylene and thelike. It is to be understood that where cyclic moieties are intended, atleast three carbons in said alkylene must be present. Such cyclicmoieties include cyclopropylene, cyclobutylene, cyclopentylene,cyclohexylene and cycloheptylene.

As used herein, the term “alkenylene” refers to a straight or branchedchain or cyclic divalent hydrocarbon radical having a specified numberof carbon atoms and one or more carbon—carbon double bonds. Alkenylenegroups include those with two to eight carbon atoms. Examples of“alkenylene” as used herein include, but are not limited to,ethene-1,2-diyl, propene-1,3-diyl, and the like.

As used herein, the term “arylene” refers to divalent unsaturatedaromatic carboxylic radicals having a single ring, such as phenylene, ormultiple condensed rings, such as naphthylene or anthrylene. Arylenegroups include those with six to thirteen carbon atoms. Examples of“arylene” as used herein include, but are not limited to,benzene-1,2-diyl, benzene-1,3-diyl, benzene-1,4-diyl,naphthalene-1,8-diyl, and the like.

As used herein, the term “alkylene-arylene”, refers to an alkylenemoiety as defined above bonded to an arylene moiety as defined above.Examples of “alkylene-arylene”as used herein include, but are notlimited to, —CH₂-phenylene, —CH₂CH₂-phenylene, and —CH₂CH₂CH₂-phenylene.

As used herein, the term “alkynyl” refers to a straight or branchedchain or cyclic monovalent hydrocarbon radical having from two to thirtycarbons and at least one carbon-carbon triple bond. Examples of“alkynyl” as used herein include, but are not limited to, ethynyl,propynyl and butynyl.

As used herein, the term “alkylamino” means alkyl group defined as abovebonded to a primary, secondary or tertiary amino group, or saltsthereof. Examples of “alkylamino” as used herein include, but are notlimited to, —(CH₂)₁₋₁₅—NH₃, and —(CH₂)₁₋₁₅—N(CH₃)₃.

The present invention provides compounds of the formula

where R¹ is

R² is

R³, R⁸, R¹³, R²⁴, R³¹ and R³³ are independently alkyl; R⁴, R⁵, R⁷, R¹⁴,R¹⁶, R¹⁹, R²⁰, R²², R²⁵, and R³² are independently alkylene; R⁶, R¹⁵,R¹⁸, and R²⁶ are independently alkylene, alkenylene, or arylene; R⁹ isalkylene or —NR³⁴—; R¹⁰, R¹², R²⁷, and R²⁹ are independently alkylene oralkylene-arylene; R¹¹ and R²⁸ are independently alkynyl; R¹⁷ is2,5-dioxo-1-pyrrolidinyl; R²¹ is alkylamino or alkyl; R²³ is arylene;R³⁰ is alkylene or —NR³⁶—; R³⁴, and R³⁶ are independently H or C₁-C₄alkyl; p is 1-5; and n is 1-20; and where R¹ and R² are not the same.

Examples of R¹ when R¹ is alkyl include C₁-C₂₀ alkyl, C₆-C₁₈ alkyl, andC₁₂-C₁₆ alkyl. Additional examples of R¹ when R¹ is alkyl includedodecyl and hexadecyl.

Examples of R² when R² is alkylamino include C₁-C₂₀ alkylamino, C₆-C₁₈alkylamino, and C₁₁-C₁₆ alkylamino. Additional examples of R² when R² isalkylamino include (C₁-C₁₈ alkyl)-NR³⁵ ₃X, where R³⁵ is H or C₁-C₄alkyl, such as methyl, for example, and X is a suitable counterion, suchas F⁻, Br⁻, Cl⁻, I⁻, OH⁻, N₃ ⁻, HCO₃ ⁻, or CN⁻, for example. Furtherexamples of R² when R² is alkylamino include —(CH₂)₁₁—NH₃X, where X isdefined as above, —(CH₂)₁₁—N(CH₃)₃X, where X is defined above,—(CH₂)₁₅—N(CH₃)₃X, where X is defined above, and —(CH₂)₁₅—NH₃X, where Xis defined above.

Examples of R³ include C₁-C₂₀ alkyl, and C₆-C₁₈ alkyl. Additionalexamples of R³ include undecyl and pentadecyl.

Examples of R⁴ include C₁-C₁₄ alkylene, and C₁-C₄ alkylene. Additionalexamples of R⁴ include methylene (—CH₂—), trimethylene, (—CH₂CH₂CH₂—),and tetramethylene (—CH₂CH₂CH₂CH₂—).

Examples of R⁵ include C₁-C₁₄ alkylene, and C₁-C₃ alkylene. Additionalexamples of R⁵ include ethylene (—CH₂CH₂—), and trimethylene(—CH₂CH₂CH₂—).

Examples of R⁶ when R⁶ is alkylene include C₁-C₁₄ alkylene, and C₁-C₃alkylene. Additional examples of R⁶ when R⁶ is alkylene include ethylene(—CH₂CH₂—), and trimethylene (—CH₂CH₂CH₂—). Examples of R⁶ when R⁶ isalkenylene include C₂-C₈ alkenylene, and C₂-C₄ alkenylene. An additionalexample of R⁶ when R⁶ is alkenylene includes ethenylene (—C═C—).Examples of R⁶ when R⁶ is arylene include C₆-C₁₃ arylene, and phenylene.An additional example of R⁶ when R⁶ is arylene is benzene-1,2-diyl.

Examples of R⁷ include C₁-C₁₄ alkylene, and C₂-C₉ alkylene. Additionalexamples of R⁷ include ethylene (—CH₂CH₂—), trimethylene (—CH₂CH₂CH₂—),tetramethylene (—CH₂CH₂CH₂CH₂—), pentamethylene (—CH₂CH₂CH₂CH₂CH₂—),hexamethylene (—CH₂CH₂CH₂CH₂CH₂CH₂—), heptamethylene(—CH₂CH₂CH₂CH₂CH₂CH₂—), octamethylene (—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—), andnonamethylene (—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—).

Examples of R⁸ include C₁-C₁₆ alkyl, and C₁-C₈ alkyl. Additionalexamples of R⁸ include butyl, pentyl and hexyl.

R⁹ is independently alkylene or —NR³⁴—, where R³⁴ is H or C₁-C₄ alkyl.

Examples of R⁹ when R⁹ is alkylene include C₁-C₁₄ alkylene, and C₁-C₃alkylene, such as methylene (—CH₂—) for example. Examples of R⁹ when R⁹is —NR³⁴— include —NH—, —N(CH₂CH₃)—, and —N(CH₃)—.

Examples of R¹⁰ when R¹⁰ is alkylene include C₁-C₁₄ alkylene, and C₁-C₈alkylene. Additional examples of R¹⁰ when R¹⁰ is alkylene includemethylene (—CH₂—), ethylene (—CH₂CH₂—), trimethylene (—CH₂CH₂CH₂—),tetramethylene (—CH₂CH₂CH₂CH₂—), —C(CH₃)₂—, and —CH((CH₂)₁₋₄—CH₃)—.Examples of R¹⁰ when R¹⁰ is alkylene-arylene include (C₁-C₁₄alkylene)-arylene, and (C₁-C₁₄ alkylene)-phenylene. An additionalexample of R¹⁰ when R¹⁰ is alkylene-arylene includes —CH₂-phenylene.

Examples of R¹¹ include C₂-C₃₀ alkynyl, and C₂₀-C₂₅ alkynyl. Additionalexamples of R¹¹ include C₂-C₃₀ alkynyl having at least two carbon-carbontriple bonds (—C≡C—), and C₂₀-C₂₅ alkynyl having at least twocarbon-carbon triple bonds. Further examples of R¹¹ include C₂₂ alkynylhaving at least two carbon-carbon triple bonds, C₂₄ alkynyl having atleast two carbon-carbon triple bonds. Yet further examples of R¹¹include —(CH₂)₈—C≡C—C≡C—(CH₂)₉CH₃, and —(CH₂)₈—C≡C—C≡C—(CH₂)₁₁CH₃.

Examples of R¹² when R¹² is alkylene include C₁-C₁₄ alkylene, and C₁-C₈alkylene. Additional examples of R¹² when R¹² is alkylene includemethylene (—CH₂—), ethylene (—CH₂CH₂—), trimethylene (—CH₂CH₂CH₂—),tetramethylene (—CH₂CH₂CH₂CH₂—), —C(CH₃)₂—, and —CH((CH₂)₁₋₄—CH₃)—.Examples of R¹² when R¹² is alkylene-arylene include (C₁-C₁₄alkylene)-arylene, and (C₁-C₁₄ alkylene)-phenylene. An additionalexample of R¹² when R¹² is alkylene-arylene includes —CH₂-phenylene.

Examples of R¹³ include C₁-C₄ alkyl, such as methyl for example.

Examples of R¹⁴ include C₁-C₄ alkylene, such as ethylene (—CH₂CH₂—) forexample.

Examples of R¹⁵ when R¹⁵ is alkylene include C₁-C₁₄ alkylene, and C₁-C₃alkylene. Additional examples of R¹⁵ when R¹⁵ is alkylene includeethylene (—CH₂CH₂—), and trimethylene (—CH₂CH₂CH₂—). Examples of R¹⁵when R¹⁵ is alkenylene include C₂-C₈ alkenylene, and C₂-C₄ alkenylene.An additional example of R¹⁵ when R¹⁵ is alkenylene includes ethenylene(—C═C—). Examples of R¹⁵ when R¹⁵ is arylene include C₆-C₁₃ arylene, andphenylene. An additional example of R¹⁵ when R¹⁵ is arylene isbenzene-1,4-diyl.

Examples of R¹⁶ include C₁-C₁₄ alkylene, and C₂-C₉ alkylene. Additionalexamples of R¹⁶ include ethylene (—CH₂CH₂—), trimethylene (—CH₂CH₂CH₂—),tetramethylene (—CH₂CH₂CH₂CH₂—), pentamethylene (—CH₂CH₂CH₂CH₂CH₂—),hexamethylene (—CH₂CH₂CH₂CH₂CH₂CH₂—), heptamethylene(—CH₂CH₂CH₂CH₂CH₂CH₂—), octamethylene (—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—), andnonamethylene (—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—).

Examples of R¹⁷ include groups that activate the neighboring ester grouptoward acyl transfer. Such ester activating groups includepentafluorophenol, pentachlorophenol, 2,4,6-trichlorophenol,3-nitrophenol, N-hydroxysuccinimide, N-hydroxyphthalimide and thosedisclosed in M. Bodanszky, “Principles of Peptide Synthesis,”(Springer-Verlag, 1984), for example. An additional example of R¹⁷ is2,5-dioxo-1-pyrrolidinyl.

Examples of R¹⁸ when R¹⁸ is alkylene include C₁-C₁₄ alkylene, and C₁-C₃alkylene. Additional examples of R¹⁸ when R¹⁸ is alkylene includeethylene (—CH₂CH₂—), and trimethylene (—CH₂CH₂CH₂—). Examples of R¹⁸when R¹⁸ is alkenylene include C₂-C₈ alkenylene, and C₂-C₄ alkenylene.An additional example of R¹⁸ when R¹⁸ is alkenylene includes ethenylene(—C═C—). Examples of R¹⁸ when R¹⁸ is arylene include C₆-C₁₃ arylene, andphenylene. An additional example of R¹⁸ when R¹⁸ is arylene isbenzene-1,2-diyl.

Examples of R¹⁹ include C₁-C₁₄ alkylene, and C₂-C₉ alkylene. Additionalexamples of R¹⁹ include ethylene (—CH₂CH₂—), trimethylene (—CH₂CH₂CH₂—),tetramethylene (—CH₂CH₂CH₂CH₂—), pentamethylene (—CH₂CH₂CH₂CH₂CH₂—),hexamethylene (—CH₂CH₂CH₂CH₂CH₂CH₂—), heptamethylene(—CH₂CH₂CH₂CH₂CH₂CH₂—), octamethylene (—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—), andnonamethylene (—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—).

Examples of R²⁰ include C₁-C₁₄ alkylene, C₁-C₉ alkylene, and C₁-C₄alkylene. Additional examples of R²⁰ include methylene (—CH₂—), ethylene(—CH₂CH₂—), trimethylene (—CH₂CH₂CH₂—), tetramethylene (—CH₂CH₂CH₂CH₂—),pentamethylene (—CH₂CH₂CH₂CH₂CH₂—), hexamethylene(—CH₂CH₂CH₂CH₂CH₂CH₂—), heptamethylene (—CH₂CH₂CH₂CH₂CH₂CH₂—),octamethylene (—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—), and nonamethylene(—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—).

Examples of R²¹ when R²¹ is alkylamino include C₁-C₂₀ alkylamino, C₆-C₁₈alkylamino, and C₁₁-C₁₆ alkylamino. Additional examples of R²¹ when R²¹is alkylamino include (C₁-C₁₈ alkyl)-NR³⁵ ₃X, where R³⁵ is H or C₁-C₄alkyl, such as methyl, for example, and X is a suitable counterion, suchas F⁻, Br⁻, Cl⁻, I⁻, OH⁻, N₃ ⁻, HCO₃ ⁻, and CN⁻, for example. Furtherexamples of R²¹ when R²¹ is alkylamino include —(CH₂)₁₀—NH₃X, where X isdefined as above, —(CH₂)₁₀—N(CH₃)₃X, where X is defined above,—(CH₂)₁₄—N(CH₃)₃X, where X is defined above, and —(CH₂)₁₄—NH₃X, where Xis defined above. Examples of R²¹ when R²¹ is alkyl include C₁-C₂₀alkyl, C₆-C₁₈ alkyl, and C₁₀-C₁₇ alkyl. Additional examples of R²¹ whenR²¹ is alkyl include decyl, undecyl, tridecyl, tetradecyl, pentadecyl,heptadecyl.

Examples of R²² include C₁-C₁₄ alkylene, and C₂-C₉ alkylene. Additionalexamples of R²² include ethylene (—CH₂CH₂—), trimethylene (—CH₂CH₂CH₂—),and tetramethylene.

Examples of R²³ include C₆-C₁₃ arylene, and phenylene. An additionalexample of R²³ when R²³ is arylene is benzene-1,4-diyl.

Examples of R²⁴ include C₁-C₂₀ alkyl, and C₆-C₁₈ alkyl. Additionalexamples of R²⁴ include methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, and dodecyl.

Examples of R²⁵ include C₁-C₁₄ alkylene, and C₂-C₉ alkylene. Additionalexamples of R²⁵ include ethylene (—CH₂CH₂—), trimethylene (—CH₂CH₂CH₂—),tetramethylene (—CH₂CH₂CH₂CH₂—), pentamethylene (—CH₂CH₂CH₂CH₂CH₂—),hexamethylene (—CH₂CH₂CH₂CH₂CH₂CH₂—), heptamethylene(—CH₂CH₂CH₂CH₂CH₂CH₂—), octamethylene (—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—), andnonamethylene (—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—).

Examples of R²⁶ when R²⁶ is alkylene include C₁-C₁₄ alkylene, and C₁-C₃alkylene. Additional examples of R²⁶ when R²⁶ is alkylene includeethylene (—CH₂CH₂—), and trimethylene (—CH₂CH₂CH₂—). Examples of R²⁶when R²⁶ is alkenylene include C₂-C₈ alkenylene, and C₂-C₄ alkenylene.An additional example of R²⁶ when R²⁶ is alkenylene includes ethenylene(—C═C—). Examples of R²⁶ when R²⁶ is arylene include C₆-C₁₃ arylene, andphenylene. An additional example of R²⁶ when R²⁶ is arylene isbenzene-1,2-diyl.

Examples of R²⁷ when R²⁷ is alkylene include C₁-C₁₄ alkylene, and C₁-C₈alkylene. Additional examples of R²⁷ when R²⁷ is alkylene includemethylene (—CH₂—), ethylene (—CH₂CH₂—), trimethylene (—CH₂CH₂CH₂—),tetramethylene (—CH₂CH₂CH₂CH₂—), —C(CH₃)₂—, and —CH((CH₂)₁₋₄CH₃)—.Examples of R²⁷ when R²⁷ is alkylene-arylene include (C₁-C₁₄alkylene)-arylene, and (C₁-C₁₄ alkylene)-phenylene. An additionalexample of R²⁷ when R²⁷ is alkylene-arylene includes —CH₂-phenylene.

Examples of R²⁸ include C₂-C₃₀ alkynyl, and C₂₀-C₂₅ alkynyl. Additionalexamples of R²⁸ include C₂-C₃₀ alkynyl having at least two carbon-carbontriple bonds (—C≡C—), and C₂₀-C₂₅ alkynyl having at least twocarbon-carbon triple bonds. Further examples of R²⁸ include C₂₂ alkynylhaving at least two carbon-carbon triple bonds, C₂₄ alkynyl having atleast two carbon-carbon triple bonds. Yet further examples of R²⁸include —(CH₂)₈—C≡C—C≡C—(CH₂)₉CH₃, and —(CH₂)₈—C≡C—C≡C—(CH₂)₁₁CH₃.

Examples of R²⁹ when R²⁹ is alkylene include C₁-C₁₄ alkylene, and C₁-C₈alkylene. Additional examples of R²⁹ when R²⁹ is alkylene includemethylene (—CH₂—), ethylene (—CH₂CH₂—), trimethylene (—CH₂CH₂CH₂—),tetramethylene (—CH₂CH₂CH₂CH₂—), —C(CH₃)₂—, and —CH((CH₂)₁₋₄CH₃)—.Examples of R²⁹ when R²⁹ is alkylene-arylene include (C₁-C₁₄alkylene)-arylene, and (C₁-C₁₄ alkylene)-phenylene. An additionalexample of R²⁹ when R²⁹ is alkylene-arylene includes —CH₂-phenylene.

R³⁰ is independently alkylene or —NR³⁶—, where R³⁶ is H or C₁-C₄ alkyl.

Examples of R³⁰ when R³⁰ is alkylene include C₁-C₁₄ alkylene, and C₁-C₃alkylene, such as methylene (—CH₂—) for example. Examples of R³⁰ whenR³⁰ is —NR³⁶— include —NH, —N(CH₂CH₃)—, and —N(CH₃)—.

Examples of R³¹ include C₁-C₁₆ alkyl, and C₁-C₈ alkyl. Additionalexamples of R³¹ include butyl, pentyl and hexyl.

Examples of R³² include C₁-C₁₄ alkylene, and C₂-C₉ alkylene. Additionalexamples of R³² include ethylene (—CH₂CH₂—), trimethylene (—CH₂CH₂CH₂—),tetramethylene (—CH₂CH₂CH₂CH₂—), pentamethylene (—CH₂CH₂CH₂CH₂CH₂—), andhexamethylene (—CH₂CH₂CH₂CH₂CH₂CH₂—).

Examples of R³³ include C₁-C₂₀ alkyl, C₆-C₁₈ alkyl, and C₁₀-C₁₆ alkyl.Additional examples of R³³ include dodecyl, tetradecyl, hexadecyl, andoctadecyl.

Compounds of the present invention also include those where p can be 1or 2 and n can be 1-20, 3-17, 6-14, or 9-11.

The invention is inclusive of the compounds described herein includingisomers, such as structural isomers and geometric isomers, salts,solvates, polymorphs and the like.

The synthesis of the diacetylenic materials disclosed herein are adaptedform published procedures such as those in Xu, Z.; Byun, H. S.; Bittman,R.; J. Org. Chem., 1991, 56, 7183-7186. For example, the diacetylenesthe formula I can be prepared as shown in Scheme 1 where n is typically1 to 14. Compounds of the formula I can be prepared from compounds ofthe formula II via anion exchange with an anion exchange resin, such as“Dowex” anion exchange resin (available from Aldrich Chemical,Milwaukee, Wis.) for example, and a suitable eluent, such as aqueoussodium chloride for example.

Compounds of formula II can be prepared from compounds of formula III byreaction with an appropriate alkylating agent in a suitable solvent.Suitable methylating agents include methyl iodide for example andsuitable solvents include acetonitrile. The aforesaid reaction is runfor a period of time from 1 hour to 96 hours, generally 20 hours, at atemperature from 20° C. to 70° C., generally from 20° C. to 50° C., inthe presence of a base such as sodium carbonate for example.

Compounds of formula III can be prepared from compounds of formula IV byreaction with an appropriate reducing agent in a suitable solventfollowed by protonation via a suitable acid to afford the salt. Suitablereducing agents include lithium aluminum hydride, sodium borohydride,and triphenylphosphine, for example. Suitable solvents include ether,tetrahydrofuran, dichloromethane, chloroform, and mixtures of thesesolvents with water, for example. Suitable acids include mineral acidssuch as HCl for example. The aforesaid reaction is run for a period oftime from 1 hour to 96 hours, generally 20 hours, at a temperature from0° C. to 40° C., generally from 10° C. to 25° C.

Compounds of formula IV can be prepared from compounds of formula VI viacompounds of formula V. A compound of formula VI is reacted with areagent suitable for the desilylation of a protected hydroxyl group inthe presence of a suitable solvent. Such deprotecting reagents includetetrabutylammonium fluoride and those described in Greene and Wuts,“Protecting Groups in Organic Synthesis,” (John Wiley & Son Press, 2ndEd), for example. Suitable solvents include ether, tetrahydrofuran,dichloromethane, and chloroform, for example. The aforesaid reaction isrun for a period of time from 0.5 hours to 5 hours, generally 1 hour, ata temperature from 0° C. to 40° C., generally from 10° C. to 25° C. Theunpurified deprotected alcohol V is then reacted with a sulfonyl halidein the presence of a solvent. Suitable sulfonyl halides includemethanesulfonyl chloride or p-toluenesulfonyl chloride. The aforesaidreaction is typically run for a period of time from 0.5 hours to 5hours, generally 2 hours, at a temperature from 0° C. to 40° C.,generally from 10° C. to 25° C., in the presence of a base such astrialkylamine or pyridine base. The resulting unpurified sulfonylderivative is then reacted with sodium azide in a suitable solvent suchas DMF. The aforesaid reaction is typically run for a period of timefrom 1 hour to 48 hours, generally 20 hours, at a temperature from 20°C. to 100° C., generally from 70° C. to 90° C., in the presence of abase such as trialkylamine or pyridine base.

Compounds of formula VI can be prepared from compounds of formula VII byreaction with a suitable alkyl halide or alkyl tosylate in a suitablesolvent. Useful haloalkanes include primary alkyl halides such as1-bromooctane, 1-bromododecane or 1-bromohexadecane. Suitable solventsinclude tetrahydrofuran, dichloromethane, and chloroform, for example.The aforesaid reaction is typically run for a period of time from 0.5hours to 48 hours, generally 1 hour, at a temperature from −78° C. to40° C., generally from −78° C. to −50° C., in the presence of a basesuch as an alkyl lithium base for example.

Compounds of formula VII can be prepared from compounds of formula VIIIby reaction with a base such as an alkyl lithium base in a suitablesolvent. Suitable alkyl lithium bases include methyl lithium. Suitablesolvents include tetrahydrofuran, dichloromethane, and ether, forexample. The aforesaid reaction is typically run for a period of timefrom 0.5 hours to 48 hours, generally 1 hour, at a temperature from −78°C. to 40° C., generally from −78° C. to −50° C. The resulting reactionmixture is then added to a solution of a suitable silyl protectedhydroxy alkyl halide, such as those of formula IX for example, in asuitable solvent. Suitable solvents include tetrahydrofuran,dichloromethane, and chloroform, for example. The aforesaid reaction istypically run for a period of time from 0.5 hours to 48 hours, generally1 hour, at a temperature from −78° C. to 40° C., generally from −20° C.to 0° C. The resulting compound was then reacted with tetrabutylammoniumfluoride in a suitable solvent. Suitable solvents includetetrahydrofuran, dichloromethane, and chloroform, for example. Theaforesaid reaction is typically run for a period of time from 0.5 hoursto 48 hours, generally 20 hours, at a temperature from −78° C. to 40°C., generally from 0° C. to 25° C.

Silyl protected hydroxy alkyl halides, such as those of formula IX canbe purchased commercially or prepared by reacting a suitablehaloalcohol, such as those of formula X for example, with TBDMSCI in asuitable solvent. Suitable solvents include tetrahydrofuran,dichloromethane, and chloroform, for example. The aforesaid reaction istypically run for a period of time from 0.5 hours to 48 hours, generally1 hour, at a temperature from 0° C. to 40° C., generally from 10° C. to25° C., in the presence of a base such as imidazole for example.

Diacetylenes of the Formula XVII can be prepared as outlined in Scheme 2where n is typically 10 to 14, m is typically 1 to 4, and p is typically10-14.

Compounds of formula XVII can be prepared from compounds of formula XVIby reaction with an appropriate reducing agent in a suitable solventfollowed by protonation via a suitable acid to afford the salt. Suitablereducing agents include lithium aluminum hydride, sodium borohydride,and triphenylphosphine, for example. Suitable solvents include ether,tetrahydrofuran, dichloromethane, chloroform, and mixtures of thesesolvents with water, for example. Suitable acids include mineral acidssuch as HCl for example. The aforesaid reaction is run for a period oftime from 1 hour to 96 hours, generally 20 hours, at a temperature from0° C. to 40° C., generally from 10° C. to 25° C.

Compounds of formula XVI can be prepared from compounds of formula XV byreaction with a compound of formula XIII and a suitable acid chloride inthe presence of a suitable solvent. Suitable compounds of formula XIIIinclude any azido functionalized acid chloride that affords the desiredproduct such as 11-azidoundecanoyl chloride for example. Suitable acidchlorides include any acid chloride that affords the desired productsuch as 1-undecanoyl chloride and 1-pentadecanoyl chloride for example.Suitable solvents include ether, tetrahydrofuran, dichloromethane, andchloroform, for example. The aforesaid reaction is typically run for aperiod of time from 1 hour to 24 hours, generally 3 hours, at atemperature from 0° C. to 40° C., generally from 0° C. to 25° C., in thepresence of a base such as trialkylamine or pyridine base.

Compounds of formula XV can be prepared via oxidative coupling ofcompounds of formula XIV by reaction with copper(I) chloride in thepresence of a suitable solvent. Suitable solvents include alcohols suchas methyl alcohol for example. The aforesaid reaction is typically runfor a period of time from 24 hour to 72 hours, generally 48 hours, at atemperature from 0° C. to 40° C., generally from 0° C. to 25° C., in thepresence of oxygen and a base such as pyridine.

Compounds of formula XIII can be prepared from compounds of formula XIvia compounds of the formula XII as outlined in the Canadian Journal ofChemistry, 1999, 146-154. For example commercially available halogenderivatized carboxylic acids of the formula XI are reacted with sodiumazide in the presence of a suitable solvent such as DMF. The aforesaidreaction is typically run for a period of time from 1 hour to 48 hours,generally 20 hours, at a temperature from 20° C. to 100° C., generallyfrom 70° C. to 90° C. The unpurified azido derivatized carboxylic acidis then reacted with oxalyl chloride in the presence of a suitablesolvent such as benzene for example. The aforesaid reaction is typicallyrun for a period of time from 1 hour to 48 hours, generally 20 hours, ata temperature from 0° C. to 50° C., generally from 0° C. to 25° C.

Diacetylenes of the Formula XXIII can be prepared as outlined in Scheme3 where n is typically 1 to 4 and m is typically 10 to 14.

Compounds of formula XXIII can be prepared via oxidation from compoundsof formula XXII by reaction with a suitable oxidizing agent in asuitable solvent such as DMF for example. Suitable oxidizing agentsinclude Jones reagent and pyridinium dichromate for example. Theaforesaid reaction is typically run for a period of time from 1 hour to48 hours, generally 8 hours, at a temperature from 0° C. to 40° C.,generally from 0° C. to 25° C.

Compounds of formula XXII can be prepared from compounds of formula XXIby reaction with a suitable acid chloride. Suitable acid chloridesinclude any acid chloride that affords the desired product such aslauroyl chloride, 1-dodecanoyl chloride, 1-tetradecanoyl chloride,1-hexadecanoyl chloride, and 1-octadecanoyl chloride for example.Suitable solvents include ether, tetrahydrofuran, dichloromethane, andchloroform, for example. The aforesaid reaction is typically run for aperiod of time from 1 hour to 24 hours, generally 3 hours, at atemperature from 0° C. to 40° C., generally from 0° C. to 25° C., in thepresence of a base such as trialkylamine or pyridine base.

Compounds of formula XXI are either commercially available (e.g. where nis 1-4) or can be prepared from compounds of the formula XVIII viacompounds XIX and XX as outlined in Scheme 3 and disclosed in Abrams,Suzanne R.; Shaw, Angela C. “Triple-bond isomerizations: 2- to9-decyn-1-ol,” Org. Synth. (1988), 66 127-31 and Brandsma, L.“Preparative Acetylenic Chemistry,” (Elsevier Pub. Co.: New York, 1971),for example.

Diacetylenic compounds as disclosed herein can also be prepared byreacting compounds of formula XXII with an anhydride such as succinic,glutaric, or phthalic anhydride in the presence of a suitable solventsuch as toluene. The aforesaid reaction is typically run for a period oftime from 1 hour to 24 hours, generally 15 hours, at a temperature from50° C. to 125° C., generally from 100° C. to 125° C.

The diacetylenic compounds as disclosed herein self assemble in solutionto form ordered assemblies that can be polymerized using any actinicradiation such as, for example, electromagnetic radiation in the UV orvisible range of the electromagnetic spectrum. Polymerization of thediacetylenic compounds disclosed herein result in polymerizationreaction products that have a color in the visible spectrum less than570 nm, between 570 nm and 600 nm, or greater than 600 nm depending ontheir conformation and exposure to external factors. Typically,polymerization of the diacetylenic compounds disclosed herein result inmeta-stable blue phase polymer networks that include a polydiacetylenebackbone. These meta-stable blue phase polymer networks undergo a colorchange from bluish to reddish-orange upon exposure to external factorssuch as heat, a change in solvent or counterion, if available, orphysical stress for example. Polymerization products of some of thediacetylenic compounds disclosed herein can exhibit a reversible colorchange and/or a three state color change. For example, afterpolymerization the resulting blue-phase polymer network can change colorto a reddish-orange state upon exposure to heat, a change in solvent orcounterion, or physical stress. This reddish-orange polymer network canthen change color to a yellowish-orange state upon further exposure toheat, a change in solvent or counterion, or physical stress.Additionally, polymer networks disclosed herein can cycle between thesereddish-orange and yellowish-orange states in a reversible manner.

The ability of the diacetylenic compounds and their polymerizationproducts disclosed herein to undergo a visible color change uponexposure to a variety of elements, including ultraviolet light, physicalstress, a change in solvent and a change in counter ion, for example,make them ideal candidates for the preparation of various sensingdevices. Such sensing devices can employ the diacetylenic compounds andtheir polymerization products disclosed herein in solution or in theirsolid state. For example, the diacetylenic compounds and theirpolymerization products disclosed herein can be used as ultravioletlight dosimeters to measure exposure to ultraviolet radiation. Thediacetylenic compounds disclosed herein respond to UV-A, UV-B, and UV-Clight in a manner similar to the human skin, thereby closely matchingthe erythemal response. Thus, such dosimeters could serve as a warningto a user against excessive solar UV exposure.

The structural requirements of diacetylenic molecule for a given sensingapplication are typically application specific. Features such as overallchain length, solubility, polarity, crystallinity, and the presence offunctional groups for further molecular modification all cooperativelydetermine a diacetylenic molecule's ability to serve as a useful sensingmaterial.

The diacetylenic compounds disclosed herein possess the capabilitiesdescribed above and can be easily and efficiently polymerized intonetworks that undergo the desired color changes in response to heat, achange in solvent or counterion, if available, or physical stress. Thediacetylenic compounds disclosed herein require mild conditions for theordering of the compounds in solution. With respect to diacetyleniccompounds of the present invention that include an ammonium moiety theuse of high temperatures and high intensity probe sonication is notrequired. Additionally, the diacetylenic compounds disclosed hereinallow for the incorporation of large excesses of unpolymerizable monomerwhile still forming a stable, polymerizable solution. The diacetyleniccompounds disclosed herein can be synthesized in a rapid high-yieldingfashion, including high-throughput methods of synthesis. The presence offunctionality in the backbones of the diacetylenic compounds disclosedherein, such as heteroatoms for example, provides for the possibility ofeasy structural elaboration in order to meet the requirements of a givensensing application. The diacetylenic compounds disclosed herein can bepolymerized into the desired polydiacetylene backbone containing networkby adding the diacetylene to a suitable solvent, such as water forexample, heating or sonicating the mixture, and then irradiating thesolution with ultraviolet light, typically at a wavelength of 254 nm.Upon polymerization the solution undergoes a color change tobluish-purple.

EXAMPLES

The present invention should not be considered limited to the particularexamples described below, but rather should be understood to cover allaspects of the invention as fairly set out in the attached claims.Various modifications, equivalent processes, as well as numerousstructures to which the present invention may be applicable will bereadily apparent to those of skill in the art to which the presentinvention is directed upon review of the instant specification. Allparts, percentages, ratios, etc. in the examples and the rest of thespecification are by weight unless indicated otherwise. All solvents andreagents without a named supplier were purchased from Aldrich Chemical;Milwaukee, Wis. Water was purified by the use of a UV Milli-Q waterpurifier with a resistivity of 18.2 Mohms/cm (Millipore Corp., Bedford,Mass.).

Table of Abbreviations Abbreviation or Trade Name Description11-Bromo-1-undecanol Br(CH₂)₁₁OH Commercially available from AldrichChemical; Milwaukee, WI 11-Bromoundecanoic Br(CH₂)₁₀C(O)OH Commerciallyavailable acid from Aldrich Chemical; Milwaukee, WI TBDMSClTert-butyldimethylsilyl chloride Commercially available from AldrichChemical; Milwaukee, WI Diyne-1 Bis(trimethylsilyl)butadiynecommercially available from Gelest; Tullytown, PA THF Tetrahydrofuran1-Bromododecane Br(CH₂)₁₁CH₃ Commercially available from AldrichChemical; Milwaukee, WI TBAF Tetrabutylammonium fluoride Commerciallyavailable from Aldrich Chemical; Milwaukee, WI HMPAHexamethylphosphoramide Commercially available from Aldrich Chemical;Milwaukee, WI 1-Bromohexadecane Br(CH₂)₁₅CH₃ Commercially available fromAldrich Chemical; Milwaukee, WI Methanesulfonyl Commercially availablefrom Aldrich chloride Chemical; Milwaukee, WI CH₂Cl₂ Dichloromethane DMFDimethylformamide oxalyl chloride ClCOCOCl commercially available fromAldrich Chemical, Milwaukee, WI PDC Pyridinium dichromate, commerciallyavailable from Aldrich Chemical, Milwaukee, WI DMAP4-(dimethylamino)pyridine, commercially available from Aldrich Chemical,Milwaukee, WI KAPA Potassium 3-aminopropylamide prepared according toAbrams, S. R.; Shaw, A. C. Organic Syntheses, 1988, 66, 127-131.

Example 1 Preparation of CH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁NR₃X Step 1:Preparation of Br(CH₂)₁₁OSi(Me₂(CMe₃))

In a glass reaction vessel, a solution of 3.0 grams (12 mmol)11-Bromo-1-undecanol in 40 milliliters CH₂Cl₂ was prepared and to thiswas added 2.7 grams (18 mmol) TBDMSC1 and 1.2 grams (18 mmol) imidazole.The resulting mixture was stirred at room temperature for 18 h, and thereaction was worked up using dichloromethane and brine. Thedichloromethane layer was dried (MgSO₄), filtered, and concentrated toyield 4.5 grams of Br(CH₂)₁₁OSi(Me₂(CMe₃)).

Step 2: Preparation of HC—C≡C(CH₂)₁₁OSi(Me₂(CMe₃))

In a glass reaction vessel, 710 milligrams (3.6 mmol) Diyne-1 wasdissolved in 15 milliliters THF and cooled to −78° C. To this stirredsolution was added 1 equivalent of methyl lithium (as complex withlithium bromide, 1.5 molar solution in Et₂O). The mixture was stirredfor 30 minutes and added via cannula to a −15° C. solution of 1.47 grams(4.0 mmol) Br(CH₂)₁₁OSi(Me₂(CMe₃)) in 8 milliliters HMPA and 16milliliters THF. The resulting mixture was worked up using pentane andbrine. The pentane layer was dried (MgSO₄), filtered, and concentrated.To the resulting solid was added 3.6 milliliters TBAF (1 molar solutionin THF) dissolved in 35 milliliters THF and 1 milliliters water. Thesolution was filtered and concentrated under vacuum to provide a crudesolid. This material was purified using column chromatography elutingwith 3% by volume of ethyl acetate in hexanes to yield 510 milligramsHCC—C≡C(CH₂)₁₁OSi(Me₂(CMe₃)).

Step 3: Preparation of CH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁OSi(Me₂(CMe₃))

In a glass reaction vessel, 1.31 grams (3.9 mmol)HC≡C—C≡C(CH₂)₁₁OSi(Me₂(CMe₃)) prepared in Step 2, was dissolved in 20milliliters THF and cooled to −78° C. To this stirred solution wasdropwise added a solution of 2.8 milliliters n-butyl lithium (1.6 molarsolution in hexanes). This solution was added via cannula to a −15° C.solution 7 milliliters of HMPA and 1.02 grams (4.10 mmol)1-Bromododecane in 25 milliliters THF. The resulting mixture was workedup using heptane and brine. The heptane layer was dried (MgSO₄),filtered and concentrated. This material was purified using columnchromatography eluting with 10% by volume of dichloromethane in hexanesto yield 680 milligrams CH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁OSi(Me₂(CMe₃)).

Step 4: Preparation of Compound 1A: CH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁NH₃Cl

In a glass reaction vessel, 650 milligrams (1.3 mmol)CH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁OSi(Me₂(CMe₃)) was dissolved in 6.5milliliters THF. To this stirred solution was added 2.0 milliliters TBAF(1 molar solution in THF). After 1 h of stirring, the reaction mixturewas filtered and concentrated to 520 milligrams ofCH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁OH which was used without furtherpurification. In a glass reaction vessel, theCH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁OH was dissolved in 6.5 milliliters CH₂Cl₂and 150 μL (2.0 mmol) methanesulfonyl chloride and 360 μL (2.6 mmol)triethyl amine were added. The reaction was stirred for 2 h and workedup using CH₂Cl₂ and brine. The CH₂Cl₂ layer was dried (MgSO₄), filtered,and concentrated to 680 milligrams ofCH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁OS(O₂)CH₃ which was used without furtherpurification. In a glass reaction vessel, theCH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁OS(O₂)CH₃ was dissolved in 6.5 millilitersDMF and 570 milligrams (8.8 mmol) sodium azide was added. The reactionwas stirred for 20 h and worked up using pentane and brine. The pentanelayer was dried (MgSO₄), filtered and concentrated. This material waspurified using column chromatography eluting with 9% dichloromethane inhexanes to yield 260 milligrams of CH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁N₃. In aglass reaction vessel, the CH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁N₃ was dissolvedin 10 milliliters THF and 0.5 milliliters water and 330 milligrams (1.3mmol) triphenyl phosphine was added. After 20 h of stirring, hydrogenchloride gas was bubbled through the mixture for 30 seconds. Theresulting solid was filtered and washed with diethyl ether to yield 190milligrams CH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁NH₃Cl.

Step 5: Preparation of Compound 1B: CH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁NMe₃I

In a glass reaction vessel, 55 milligrams (0.13 mmol)CH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁NH₃Cl was dissolved in 5 millilitersacetonitrile and 100 μL (1.6 mmol) methyl iodide and 170 milligrams (1.6mmol) sodium carbonate. The solution was stirred at room temperature for20 h and filtered to yield 65 milligramsCH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁NMe₃I.

Step 6: Preparation of Compound 1C: CH₃(CH₂)₁₀CH₂C≡C—C≡C(CH₂)₁₁NMe₃Cl

A sample of Compound 1B was converted to Compound 1C by passing itthrough a Dowex anion exchange resin with sodium chloride solution.

Example 2 Preparation of CH₃(CH₂)₁₄—CH₂C≡C—C≡C(CH₂)₁₁NR₃X Step 1:Preparation of Br(CH₂)₁₁OSi(Me₂(CMe₃))

The same procedure described in Example 1 Step 1 was followed.

Step 2: Preparation of HC≡C—C≡C(CH₂)₁₁OSi(Me₂(CMe₃))

The same procedure described in Example 1 Step 2 was followed.

Step 3: Preparation of CH₃(CH₂)₁₄—CH₂C≡C—C≡C(CH₂)₁₁OSi(Me₂(CMe₃))

The same procedure described in Example 1 Step 3 was followed with theexception that 1-Bromohexadecane was used instead of 1-Bromododecane.

Step 4: Preparation of Compound 2A: CH₃(CH₂)₁₄—CH₂C≡C—C≡C(CH₂)₁₁NH₃Cl

The same procedure described in Example 1 Step 4 was followed.

Step 5: Preparation of Compound 2B: CH₃(CH₂)₁₄—CH₂C≡C—C≡C(CH₂)₁₁NMe₃I

The same procedure described in Example 1 Step 5 was followed.

Step 6: Preparation of Compound 2C: CH₃(CH₂)₁₄—CH₂C≡C—C≡C(CH₂)₁₁NMe₃Cl

The same procedure described in Example 1 Step 6 was followed.

Example 3 Preparation of CH₃(CH₂)₁₀C(O)OCH₂C≡C—C≡CCH₂OC(O)(CH₂)₁₀NH₃ClStep 1: Preparation of HOCH₂C≡C—C≡CCH₂OH

Oxidative coupling of 3-Propyn-1-ol (HOCH₂C≡CH) was carried out in aglass reaction vessel by dissolving 122 grams (2.26 mol) 2-Propyn-1-olin 70 milliliters pyridine and adding 11.1 grams (112 mmol) CuClfollowed by the addition of 220 milliliters methyl alcohol. The reactionwas stirred for 48 h in the presence of oxygen. The reaction was workedup using concentrated HCl and ethyl acetate. The ethyl acetate layer wasdried (MgSO₄), filtered and concentrated to yield 61 gramsHOCH₂C≡C—C≡CCH₂OH.

Step 2: Preparation of N₃(CH₂)₁₀C(O)Cl

In a glass reaction vessel, 10.6 grams (40 mmol) of 11-Bromoundecanoicacid was dissolved in 225 milliliters DMF and 26 grams (400 mmol) sodiumazide was added. The resulting stirred mixture was heated to 80° C. for16 h, and then the reaction mixture was worked up with ether and brine.The ether layer was dried (MgSO₄), filtered, and concentrated to 9.5grams of N₃(CH₂)₁₀C(O)OH as a pale yellow oil which was used withoutpurification. In a glass reaction vessel, the N₃(CH₂)₁₀C(O)OH wasdissolved in 120 milliliters benzene and 12.7 grams (100 mmol) oxalylchloride was added. The reaction was allowed to stir for 20 h, at whichtime the volatiles were removed in vacuo. The resulting residue wasdissolved in pentane and filtered in a nitrogen atmosphere to removesolids. Concentration of the filtrate afforded N₃(CH₂)₁₀C(O)Cl as aclear, yellow oil.

Step 3: Preparation of CH₃(CH₂)₁₀C(O)OCH₂C≡C—C≡CCH₂OC(O)(CH₂)₁₀NH₃Cl

In a glass reaction vessel, 400 milligrams (3.75 mmol) HOCH₂C≡C—C≡CCH₂OHprepared in Step 1, was dissolved in a mixture of 25 milliliters THF and1 milliliters pyridine. To this stirred solution was added 1.0 gram (4.1mmol) N₃(CH₂)₁₀C(O)Cl prepared in Step 2, and 950 μL (4.1 mmol)CH₃(CH₂)₁₀C(O)Cl. The resulting mixture was stirred for 3 h,concentrated, dissolved into hexanes and filtered to remove the salts.The filtrate was concentrated and purified using column chromatographyeluting with 10% by volume of ethyl acetate in hexanes to yield 750milligrams CH₃(CH₂)₁₀C(O)OCH₂C≡C—C≡CCH₂OC(O)(CH₂)₁₀N₃. In a glassreaction vessel, 280 milligrams (0.56 mmol)CH₃(CH₂)₁₀C(O)OCH₂C≡C—C≡CCH₂OC(O)(CH₂)₁₀N₃ was dissolved in 1milliliters water and 8 milliliters THF. To this solution, 350milligrams (1.3 mmol) triphenylphosphine was added. After 20 h ofstirring, hydrogen chloride gas was bubbled through the mixture for 30seconds. The resulting solid was filtered and washed with diethyl etherto yield 150 milligrams CH₃(CH₂)₁₀C(O)OCH₂C≡C—C≡CCH₂OC(O)(CH₂)₁₀NH₃Cl.

Example 4 Preparation ofCH₃(CH₂)₁₀C(O)O(CH₂)₃C≡C—C≡C(CH₂)₃OC(O)(CH₂)₁₀NH₃Cl

Step 1: Preparation of HO(CH₂)₃C≡C—C≡C(CH₂)₃OH (also commerciallyavailable as 4,6-decadiyn-1,10-diol from GFS; Powell, Ohio)

The same procedure was followed as for Example 3 Step 1, except that4-Pentyn-1-ol (HO(CH₂)₃C≡CH) was used instead of 2-Propyn-1-ol.

Step 2: Preparation of N₃(CH₂)₁₀C(O)Cl

The same procedure was followed as for Example 3 Step 2.

Step 3: Preparation ofCH₃(CH₂)₁₀C(O)O(CH₂)₃C≡C—C≡C(CH₂)₃OC(O)(CH₂)₁₀NH₃Cl

The same procedure was followed as for Example 3 Step 3 except thatHO(CH₂)₃C≡C—C≡C(CH₂)₃OH (prepared in Step 1) was used instead ofHOCH₂C≡C—C≡CCH₂OH.

Example 5 Preparation ofCH₃(CH₂)₁₀C(O)O(CH₂)₄C≡C—C≡C(CH₂)₄OC(O)(CH₂)₁₀NH₃Cl

Step 1: Preparation of HO(CH₂)₄C≡C—C≡C(CH₂)₄OH (Also commerciallyavailable from GFS Chemicals; Powell, Ohio as 5,7-dodecadiyn-1,12-diol).

The same procedure was followed as for Example 3 Step 1, except that5-Hexyn-1-ol (HO(CH₂)₄C≡CH) was used instead of 3-Propyn-1-ol.

Step 2: Preparation of N₃(CH₂)₁₀C(O)Cl

The same procedure was followed as for Example 3 Step 2.

Step 3: Preparation ofCH₃(CH₂)₁₀C(O)O(CH₂)₄C≡C—C≡C(CH₂)₄OC(O)(CH₂)₁₀NH₃Cl

The same procedure was followed as for Example 3 Step 3 except thatHO(CH₂)₄C≡C—C≡C(CH₂)₄OH (prepared in Step 1) was used instead ofHOCH₂C≡C—C≡CCH₂OH.

Example 6 Preparation of CH₃(CH₂)₁₄C(O)OCH₂C≡C—C≡CCH₂OC(O)(CH₂)₁₀NH₃ClStep 1: Preparation of HOCH₂C≡C—C≡CCH₂OH

The same procedure was followed as for Example 3 Step 1.

Step 2: Preparation of N₃(CH₂)₁₀C(O)Cl

The same procedure was followed as for Example 3 Step 2.

Step 3: Preparation ofCH₃(CH₂)₁₄C(O)O(CH₂)₄C≡C—C≡C(CH₂)₄OC(O)(CH₂)₁₀NH₃Cl

The same procedure was followed as for Example 3 Step 3 except thatHexadecanyl chloride was used instead of Dodecanyl chloride.

Example 7 Preparation ofCH₃(CH₂)₁₄C(O)O(CH₂)₃C≡C—C≡C(CH₂)₃OC(O)(CH₂)₁₀NH₃Cl Step 1: Preparationof HO(CH₂)₃C≡C—C≡C(CH₂)₃OH

The same procedure was followed as for Example 4 Step 1.

Step 2: Preparation of N₃(CH₂)₁₀C(O)Cl

The same procedure was followed as for Example 3 Step 2.

Step 3: Preparation ofCH₃(CH₂)₁₄C(O)O(CH₂)₃C≡C—C≡C(CH₂)₃OC(O)(CH₂)₁₀NH₃Cl

The same procedure was followed as for Example 4 Step 3 except thatHexadecanyl chloride was used instead of Dodecanyl chloride.

Example 8 Preparation ofCH₃(CH₂)₁₄C(O)O(CH₂)₄C≡C—C≡C(CH₂)₄OC(O)(CH₂)₁₀NH₃Cl Step 1: Preparationof HO(CH₂)₄C≡C—C≡C(CH₂)₄OH

The same procedure was followed as for Example 5 Step 1.

Step 2: Preparation of N₃(CH₂)₁₀C(O)Cl

The same procedure was followed as for Example 3 Step 2.

Step 3: Preparation ofCH₃(CH₂)₁₄C(O)O(CH₂)₄C≡C—C≡C(CH₂)₄OC(O)(CH₂)₁₀NH₃Cl

The same procedure was followed as for Example 5 Step 3 except thatHexadecanyl chloride was used instead of Dodecanyl chloride.

Example 9

Samples of 1.0 milliMolar concentration solutions of Compounds 1A, 1B,1C, 2A, 2B, 2C in water were prepared in glass vessels, heated in a 70°C. oven for 30 minutes, bath sonicated in a Bronson Model #1510 bathsonicator (commercially available from VWR Scientific Products; WestChester, Pa.) for 30 minutes, filtered through a 0.45 micrometer syringefilter and placed in a 4° C. refrigerator for about 16 hours. Thesolutions were removed from the refrigerator and polymerized by stirringwhile irradiating beneath a 254 nanometer wavelength UV lamp(commercially available from VWR Scientific Products; West Chester, Pa.)at a distance of 3 centimeters for 10 minutes. Whether polymerizationoccurred upon irradiation and the presence or absence of a color changeis noted in Table 1. The samples in which polymerization occurred and acolor change was observed were heated to 70° C. for 15 seconds. Theresulting color change is noted in Table 1.

TABLE 1 Color of Color of polymerized Example Did polymerizationpolymerized solution after Compound occur? solution heating to 70° C. 1AYes Blue Red 1B Yes Purple Red 1C No NA NA 2A Yes Blue Red 2B Yes PurpleRed 2C No NA NA NA = Not applicable

Example 10

Samples of 1.0 milliMolar concentration solutions of the compoundsprepared in Examples 3-8 in water were prepared in glass vessels, heatedin a 70° C. oven for 30 minutes and placed in a 4° C. refrigerator forabout 16 hours. The solutions were removed from the refrigerator andpolymerized by stirring while irradiating beneath a 254 nanometerwavelength UV lamp (commercially available from VWR Scientific Products;West Chester, Pa.) at a distance of 3 centimeters for 10 minutes. Thecolor change observed upon polymerization is noted in Table 2. Thesamples were heated to 70° C. for 15 seconds and the resulting colorchange is noted in Table 2. A third color transition was produced byheating the solutions to 90° C., and this color transition, if presentis also noted in Table 2.

TABLE 2 Color of Color of polymerized Compound polymerized solutionafter Third transition Example Number solution heating to 70° C. color 3Yellow Orange NA 6 Yellow Orange NA 4 Purple Orange Yellow 7 PurpleOrange Yellow 5 Blue Red Orange 8 Blue Red Orange NA = Not applicable

Example 11

Samples of 1.0 milliMolar concentration solutions of Compound 2Bprepared in Example 2 in water were prepared in a glass vessels, heatedin a 70° C. oven for 30 minutes, bath sonicated in a Bronson Model #1510bath sonicator (commercially available from VWR Scientific Products;West Chester, Pa.) for 30 minutes, filtered through a 0.45 micrometersyringe filter and placed in a 4° C. refrigerator for about 16 hours.The solutions were removed from the refrigerator and polymerized bystirring while irradiating beneath a 254 nanometer wavelength UV lamp ata distance of 3 centimeters for 10 minutes. Salts containing otheranions were added to the solutions. The presence or absence of anobserved color change is recorded in Table 3.

TABLE 3 Anion Color Change Observed? Cl⁻ Yes Br⁻ Yes CO₃ ²⁻ Yes SO₄ ²⁻Yes N₃ ⁻ Yes I⁻ No

Example 12 Preparation of HO(O)C(CH₂)₃C≡C—C≡C(CH₂)₄O(O)C(CH₂)₁₀CH₃ Step1: Preparation of HO(CH₂)₄C≡C—C≡C(CH₂)₄O(O)C(CH₂)₁₀CH₃

In a glass reaction vessel, 600 milligrams of 5,7-dodecadiyn-1,12-diol(HO(CH₂)₄C≡C—C≡C(CH₂)₄OH), 0.275 milliliters of pyridine and 10milliliters of THF were mixed. To this solution was added 676 milligramsof lauroyl chloride and the resulting mixture was stirred for 15 hours.The mixture was then diluted with diethyl ether and washed with 0.1 NHCl and brine. The organic layer was separated, dried over MgSO₄,filtered and the solvent was removed to yield a white solid. The solidwas purified over silica gel (gradient from 25% to 50% ethyl acetate inhexanes by volume) to yield 570 milligrams ofHO(CH₂)₄C≡C—C≡C(CH₂)₄O(O)C(CH₂)₁₀CH₃ as a white solid.

Step 2: Preparation of HO(O)C(CH₂)₃C≡C—C≡C(CH₂)₄O(O)C(CH₂)₁₀CH₃

In a glass reaction vessel, 377 milligrams ofHO(CH₂)₄C≡C—C≡C(CH₂)₄O(O)C(CH₂)₁₀CH₃ prepared in Step 1 was dissolved in3 milliliters of DMF and 1.32 grams of PDC was added. The resultingmixture was stirred for 8 hours, and then worked up with water anddiethyl ether. The combined ether layers were dried over MgSO₄, filteredand the solvent was removed to yield a white solid. The solid waspurified over silica gel eluting with 25/74/1 of ethylacetate/hexanes/formic acid by volume to yield 0.21 grams ofHO(O)C(CH₂)₃C≡C—C≡C(CH₂)₄O(O)C(CH₂)₁₀CH₃ as a white solid.

Examples 13-16 Preparation ofHO(O)C(CH₂)_(a-1)C≡C—C≡C(CH₂)_(a)O(O)C(CH₂)_(b)CH₃

The same procedure described in Example 12 was followed using the dioland acid chloride in Step 1 shown in Table 4 to give the compounds withthe general structure HO(O)C(CH₂)_(a-1)C≡C—C≡C(CH₂)_(a)O(O)C(CH₂)_(b)CH₃(a and b are defined in Table 4).

TABLE 4 Exam- ple Diol, a value Acid Chloride, b value 13HO(CH₂)₃C≡C—C≡C(CH₂)₃OH, CH₃(CH₂)₁₄C(O)Cl, a = 3 b = 14 14HO(CH₂)₄C≡C—C≡C(CH₂)₄OH, CH₃(CH₂)₁₂C(O)Cl, a = 4 b = 12 15HO(CH₂)₄C≡C—C≡C(CH₂)₄OH, CH₃(CH₂)₁₄C(O)Cl, a = 4 b = 14 16HO(CH₂)₄C≡C—C≡C(CH₂)₄OH, CH₃(CH₂)₁₆C(O)Cl, a = 4 b = 16

Example 17 Preparation ofHO(O)C(CH₂)₂C(O)O(CH₂)₄C≡C—C≡C(CH₂)₄O(O)C(CH₂)₁₂CH₃ Step 1: Preparationof HO(CH₂)₄C≡C—C≡C(CH₂)₄O(O)C(CH₂)₁₂CH₃

In a glass reaction vessel, 4.99 grams of 5,7-dodecadiyn-1,12-diol(HO(CH₂)₄C≡C—C≡C(CH₂)₄OH), 2.2. grams of pyridine and 50 milliliters ofTHF were mixed. To this solution was added 6.34 grams of myristolchloride and the resulting mixture was stirred for 15 hours. The mixturewas then diluted with diethyl ether and washed with 0.1 N HCl and brine.The organic layer was separated, dried over MgSO₄, filtered and thesolvent was removed to yield a white solid. The solid was purified oversilica gel (15% by volume of ethyl acetate in dichloromethane to 100%ethyl acetate gradient) to yield 5.0 grams ofHO(CH₂)₄C≡C—C≡C(CH₂)₄O(O)C(CH₂)₁₂CH₃ as a white solid.

Step 2: Preparation ofHO(O)C(CH₂)₂C(O)O(CH₂)₄C≡C—C≡C(CH₂)₄O(O)C(CH₂)₁₂CH₃

In a sealable tube, 1.41 grams of HO(CH₂)₃C≡C—C≡C(CH₂)₄O(O)C(CH₂)₁₂CH₃prepared in Step 1, 0.435 grams of succinic anhydride, 13 milliliters oftoluene and 0.106 grams of DMAP were combined and the tube was sealed.The mixture was heated to 105° C. for 14.5 hours, the reaction wascooled to room temperature, 0.15 milliliters of water was added, thetube was resealed and again heated to 105° C. for 30 minutes. Themixture was then diluted with diethyl ether and washed with 0.1 N HCland brine. The organic layer was separated, dried over MgSO₄, filteredand the solvent was removed to yield a white solid. The solid waspurified over silica gel eluting with 10/89/1 of ethylacetate/dichloromethane/formic acid by volume to yield 1.70 grams ofHO(O)C(CH₂)₂C(O)O(CH₂)₄C≡C—C≡C(CH₂)₄O(O)C(CH₂)₁₂CH₃ as a white solid.

Examples 18-28 Preparation ofHO(O)C(CH₂)₂C(O)O(CH₂)_(a)C≡C—C≡C(CH₂)_(a)O(O)C(CH₂)_(b)CH₃

The same procedure described in Example 17 was followed using the dioland acid chloride in Step 1 shown in Table 5 to give the compounds withthe general structureHO(O)C(CH₂)₂C(O)O(CH₂)_(a)C≡C—C≡C(CH₂)_(a)O(O)C(CH₂)_(b)CH₃ (a and b aredefined in Table 5).

TABLE 5 Exam- ple Diol, a value Acid Chloride, b value 18HO(CH₂)₂C≡C—C≡C(CH₂)₂OH, CH₃(CH₂)₁₀C(O)Cl, a = 2 b = 10 19HO(CH₂)₂C≡C—C≡C(CH₂)₂OH, CH₃(CH₂)₁₂C(O)Cl, a = 2 b = 12 20HO(CH₂)₂C≡C—C≡C(CH₂)₂OH, CH₃(CH₂)₁₄C(O)Cl, a = 2 b = 14 21HO(CH₂)₂C≡C—C≡C(CH₂)₂OH, CH₃(CH₂)₁₆C(O)Cl, a = 2 b = 16 22HO(CH₂)₃C≡C—C≡C(CH₂)₃OH, CH₃(CH₂)₁₀C(O)Cl, a = 3 b = 10 23HO(CH₂)₃C≡C—C≡C(CH₂)₃OH, CH₃(CH₂)₁₂C(O)Cl, a = 3 b = 12 24HO(CH₂)₃C≡C—C≡C(CH₂)₃OH, CH₃(CH₂)₁₄C(O)Cl, a = 3 b = 14 25HO(CH₂)₃C≡C—C≡C(CH₂)₃OH, CH₃(CH₂)₁₆C(O)Cl, a = 3 b = 16 26HO(CH₂)₄C≡C—C≡C(CH₂)₄OH, CH₃(CH₂)₁₀C(O)Cl, a = 4 b = 10 27HO(CH₂)₄C≡C—C≡C(CH₂)₄OH, CH₃(CH₂)₁₄C(O)Cl, a = 4 b = 14 28HO(CH₂)₄C≡C—C≡C(CH₂)₄OH, CH₃(CH₂)₁₆C(O)Cl, a = 4 b = 16

Example 29 Preparation ofHO(O)C(CH₂)₂C(O)O(CH₂)₅C≡C—C≡C(CH₂)₅O(O)C(CH₂)₁₀CH₃ Step 1: Preparationof HO(CH₂)₅C≡C—C≡C(CH₂)₅OH

HO(CH₂)₅C≡CH was prepared by the KAPA-promoted isomerization ofHOCH₂C≡C(CH₂)₃CH₃ (prepared according to Millar, J. G.; Oehlschlager, A.C. J. Org. Chem. 1984, 49, 2332-2338) or HO(CH₂)₂C≡C(CH₂)₂CH₃(commercially available from GFS Chemicals; Powell, Ohio). Oxidativecoupling of HO(CH₂)₅C≡CH was carried out in a glass reaction vessel bydissolving 6.95 grams of HO(CH₂)₅C≡CH in pyridine/methanol (2.0milliliters/6.2 milliliters) and adding 307 grams of CuCl followed bystirring in the presence of oxygen until all the staring material wasconsumed. The reaction mixture was worked up with diethyl ether and 4NHCl, the combined organic layers were dried over MgSO₄, filtered andconcentrated. Recrystallization of the residue from 1/1hexanes/tert-butyl methyl ether to yield 5.35 grams ofHO(CH₂)₅C≡C—C≡C(CH₂)₅OH as a pink solid.

Step 2: Preparation of HO(CH₂)₅C≡C—C≡C(CH₂)₅O(O)C(CH₂)₁₀CH₃

The same procedure described in Example 17 Step 1 was followed exceptthat instead of 5,7-dodecadiyn-1,12-diol the diol prepared in Step 1above was used.

Step 3: Preparation ofHO(O)C(CH₂)₂C(O)O(CH₂)₅C≡C—C≡C(CH₂)₅O(O)C(CH₂)₁₀CH₃

The same procedure described in Example 17 Step 2 was followed.

Examples 30-32 Preparation ofHO(O)C(CH₂)₂C(O)O(CH₂)₅C≡C—C≡C(CH₂)₅O(O)C(CH₂)_(b)CH₃

The same procedure described in Example 29 was followed using the dioland acid chloride in Step 2 shown in Table 6 to give the compounds withthe general structureHO(O)C(CH₂)₂C(O)O(CH₂)₅C≡C—C≡C(CH₂)₅O(O)C(CH₂)_(b)CH₃ (b is defined inTable 6).

TABLE 6 Exam- ple Diol Acid Chloride, b value 30 HO(CH₂)₅C≡C—C≡C(CH₂)₅OHCH₃(CH₂)₁₂C(O)Cl, b = 12 31 HO(CH₂)₅C≡C—C≡C(CH₂)₅OH CH₃(CH₂)₁₄C(O)Cl, b= 14 32 HO(CH₂)₅C≡C—C≡C(CH₂)₅OH CH₃(CH₂)₁₆C(O)Cl, b = 16

Examples 33-36 Preparation ofHO(O)C(CH₂)₂C(O)O(CH₂)₆C≡C—C≡C(CH₂)₆O(O)C(CH₂)_(b)CH₃

The same procedure described in Example 29 Step 1 was followed toprepare the diol HO(CH₂)₆C≡C—C≡C(CH₂)₆OH starting from 1-heptyne. Theremaining procedure for Example 29 was followed using the diol and acidchloride in Step 2 shown in Table 7 to give the compounds with thegeneral structure HO(O)C(CH₂)₂C(O)O(CH₂)₆C≡C—C≡C(CH₂)₆O(O)C(CH₂)_(b)CH₃(b is defined in Table 7).

TABLE 7 Exam- ple Diol Acid Chloride, b value 33 HO(CH₂)₆C≡C—C≡C(CH₂)₆OHCH₃(CH₂)₁₀C(O)Cl, b = 10 34 HO(CH₂)₆C≡C—C≡C(CH₂)₆OH CH₃(CH₂)₁₂C(O)Cl, b= 12 35 HO(CH₂)₆C≡C—C≡C(CH₂)₆OH CH₃(CH₂)₁₄C(O)Cl, b = 14 36HO(CH₂)₆C≡C—C≡C(CH₂)₆OH CH₃(CH₂)₁₆C(O)Cl, b = 16

Examples 37-39 Preparation ofHO(O)C(CH₂)₂C(O)O(CH₂)₇C≡C—C≡C(CH₂)₇O(O)C(CH₂)_(b)CH₃

The same procedure described in Example 29 Step 1 was followed toprepare the diol HO(CH₂)₇C≡C—C≡C(CH₂)₇OH staring from 1-octyne. Theremaining procedure for Example 29 was followed using the diol and acidchloride in Step 2 shown in Table 8 to give the compounds with thegeneral structure HO(O)C(CH₂)₂C(O)O(CH₂)₇C≡C—C≡C(CH₂)₇O(O)C(CH₂)_(b)CH₃(b is defined in Table 8).

TABLE 8 Exam- ple Diol Acid Chloride 37 HO(CH₂)₇C≡C—C≡C(CH₂)₇OHCH₃(CH₂)₁₀C(O)Cl, b = 10 38 HO(CH₂)₇C≡C—C≡C(CH₂)₇OH CH₃(CH₂)₁₂C(O)Cl, b= 12 39 HO(CH₂)₇C≡C—C≡C(CH₂)₇OH CH₃(CH₂)₁₆C(O)Cl, b = 16

Examples 40-43 Preparation ofHO(O)C(CH₂)₂C(O)O(CH₂)₉C≡C—C≡C(CH₂)₉O(O)C(CH₂)_(b)CH₃

The same procedure described in Example 29 Step 1 was followed toprepare the diol HO(CH₂)₉C≡C—C≡C(CH₂)₉OH starting from 1-decyne. Theremaining procedure for Example 29 was followed using the diol and acidchloride in Step 2 shown in Table 9 to give the compounds with thegeneral structure HO(O)C(CH₂)₂C(O)O(CH₂)₉C≡C—C≡C(CH₂)₉O(O)C(CH₂)_(b)CH₃(b is defined in Table 9).

TABLE 9 Exam- ple Diol Acid Chloride, b value 40 HO(CH₂)₉C≡C—C≡C(CH₂)₉OHCH₃(CH₂)₁₀C(O)Cl, b = 10 41 HO(CH₂)₉C≡C—C≡C(CH₂)₉OH CH₃(CH₂)₁₂C(O)Cl, b= 12 42 HO(CH₂)₉C≡C—C≡C(CH₂)₉OH CH₃(CH₂)₁₄C(O)Cl, b = 14 43HO(CH₂)₉C≡C—C≡C(CH₂)₉OH CH₃(CH₂)₁₆C(O)Cl, b = 16

Example 44 Preparation ofHO(O)C(CH₂)₃C(O)O(CH₂)₄C≡C—C≡C(CH₂)₄O(O)C(CH₂)₁₂CH₃

The same procedure described in Example 17 was followed except that inStep 2 glutaric anhydride was used in place of succinic anhydride.

Example 45 Preparation ofHO(O)CHC═CHC(O)O(CH₂)₄C≡C—C≡C(CH₂)₄O(O)C(CH₂)₁₄CH₃

The same procedure described in Example 17 was followed except that inStep 1 CH₃(CH₂)₁₄C(O)Cl was used instead of CH₃(CH₂)₁₂C(O)Cl and in Step2 maleic anhydride was used in place of succinic anhydride.

Example 46 Preparation ofHO(O)C(1,2-C₆H₄)C(O)O(CH₂)₄C≡C—C≡C(CH₂)₄O(O)C(CH₂)₁₂CH₃

The same procedure described in Example 17 was followed except that inStep 2 phthalic anhydride was used in place of succinic anhydride.

Example 47 Preparation ofHO(O)C(CH₂)₂C(O)O(CH₂)₄C≡C—C≡C(CH₂)₄O(CH₂)₁₁CH₃ Step 1: Preparation ofHO(CH₂)₄C≡C—C≡C(CH₂)₄O(CH₂)₁₁CH₃

In a glass reaction vessel, a suspension of 120 milligrams of sodiumhydride was prepared in 10 milliliters dry DMF and 972 milligrams of5,7-dodecadiyn-1,12-diol (HO(CH₂)₄C≡C—C≡C(CH₂)₄OH), was added. Afterstirring for 5 minutes 1.31 grams of CH₃(CH₂)₁₁Br was added and theresulting mixture was stirred for 15 hours. The mixture was thenquenched by addition of saturated NH₄Cl solution and diluted with 100milliliters of diethyl ether. The organic layer was separated and washed3 times with brine, dried over MgSO₄, filtered and the solvent wasremoved to yield a yellow oil. The oil was purified over silica gel(25%-35% by volume of ethyl acetate in hexanes gradient) to yield 606milligrams of HO(CH₂)₄C≡C—C≡C(CH₂)₄O(CH₂)₁₁CH₃ as a white solid.

Step 2: Preparation of HO(O)C(CH₂)₂C(O)O(CH₂)₄C≡C—C≡C(CH₂)₄O(CH₂)₁₁CH₃

In a sealable tube, 181 milligrams of HO(CH₂)₄C≡C—C≡C(CH₂)₄O(CH₂)₁₁CH₃prepared in Step 1, 63 milligrams of succinic anhydride, 2 millilitersof toluene and 15 milligrams of DMAP were combined and the tube wassealed. The mixture was heated to 110° C. for 16 hours, the reaction wascooled to room temperature, 3 drops of water was added, the tube wasresealed and again heated to 110° C. for 30 minutes. The mixture wasthen diluted with diethyl ether and washed with 0.1 N HCl and brine. Theorganic layer was separated, dried over MgSO₄, filtered and solvent wasremoved to yield a white solid. The solid was purified over silica geleluting with 10/89/1 of ethyl acetate/dichloromethane/formic acid byvolume to yield HO(O)C(CH₂)₂C(O)O(CH₂)₄C≡C—C≡C(CH₂)₄O(CH₂)₁₁CH₃ as awhite solid.

Examples 48-52 Preparation ofHO(O)C(CH₂)₂C(O)O(CH₂)_(a)C≡C—C≡C(CH₂)_(a)O(CH₂)_(b)CH₃

The same procedure described in Example 47 was followed using the dioland alkyl bromide in Step 1 shown in Table 10 to give the compounds withthe general structureHO(O)C(CH₂)₂C(O)O(CH₂)_(a)C≡C—C≡C(CH₂)_(a)O(CH₂)_(b)CH₃ (a and b aredefined in Table 10).

TABLE 10 Exam- ple Diol, a value Alkyl Bromide, b value 48HO(CH₂)₂C≡C—C≡C(CH₂)₂OH, CH₃(CH₂)_(b)Br, b = 13 a = 4 49HO(CH₂)₂C≡C—C≡C(CH₂)₂OH, CH₃(CH₂)_(b)Br, b = 15 a = 4 50HO(CH₂)₂C≡C—C≡C(CH₂)₂OH, CH₃(CH₂)_(b)Br, b = 17 a = 4 51HO(CH₂)₂C≡C—C≡C(CH₂)₂OH, CH₃(CH₂)_(b)Br, b = 11 a = 5 52HO(CH₂)₃C≡C—C≡C(CH₂)₃OH, CH₃(CH₂)_(b)Br, b = 13 a = 5

Example 53

A sample of 10.1 milligrams of the compound prepared in Example 17 wasplaced in a glass vessel and suspended in 5 milliliters of isopropanol.The mixture was heated to boiling and 10 milliliters of 70° C. water wasadded. The resulting solution was boiled until the temperature reached95° C. indicating the nearly all of the isopropanol had boiled off. Thesolution was cooled to room temperature and then to 4° C. for 16 hours.A 2 milliliter aliquot of the solution was exposed 254 nanometer lightfor 10 minutes, producing a dark blue color indicative thatpolymerization had occurred.

1. A polymerized composition comprising the polymerization reactionproduct of at least one compound of the formula

wherein R¹ is

R² is,

R³, R⁸, R¹³, R²⁴, R³¹ and R³³ are independently C₁-C₂₀ alkyl; R⁴, R⁵,R⁷, R¹⁴, R¹⁶, R¹⁹, R²², R²⁵, and R³² are independently C₁-C₁₄ alkylene;R⁶, R¹⁵, and R¹⁸ are independently C₁-C₁₄ alkylene, or C₂-C₈ alkenylene,or C₆-C₁₃ arylene; R²⁶ is C₁-C₁₄ alkylene, or C₂-C₈ alkenylene, R⁹ isC₁-C₁₄ alkylene; R¹⁰, R¹², R²⁷, and R²⁹ are independently C₁-C₁₄alkylene or (C₁-C₁₄ alkylene)-(C₂-C₈ arylene); R¹¹ and R²⁸ areindependently C₂-C₃₀ alkynyl; R¹⁷ is an ester activating group; R²³ isC₆-C₁₃ arylene; R³⁰ is C₁-C₁₄ alkylene; p is 1-5; n is 1-20; and whereinR¹ and R² are not the same. 2-3. (canceled)
 4. The polymerizedcomposition of claim 1, wherein R²⁴ is methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, or dodecyl.
 5. The polymerizedcomposition of claim 1, wherein R³³ is dodecyl, tetradecyl, hexadecyl,or octadecyl.
 6. The polymerized composition of claim 1, wherein R⁴ ismethylene, trimethylene, or tetramethylene.
 7. (canceled)
 8. Thepolymerized composition of claim 1, wherein R⁷, R¹⁶, R¹⁹, R²⁰ and R²⁵are independently ethylene, trimethylene, tetramethylene,pentamethylene, hexamethylene, heptamethylene, octamethylene, ornonamethylene.
 9. The polymerized composition of claim 1, wherein R²⁰ ismethylene, trimethylene, or tetramethylene.
 10. The polymerizedcomposition of claim 1, wherein R²² is ethylene, trimethylene, ortetramethylene.
 11. The polymerized composition of claim 1, wherein R³²is ethylene, trimethylene, tetramethylene, pentamethylene, orhexamethylene.
 12. The polymerized composition of claim 1, wherein R⁶,R¹⁵, R¹⁸, and R²⁶ are independently ethylene, trimethylene, ethenylene,or phenylene.
 13. The polymerized composition of claim 1, wherein R⁸ andR³¹ are independently C₁-C₁₄ alkyl.
 14. (canceled)
 15. The polymerizedcomposition of claim 1, wherein R¹⁰, R¹², R²⁷, and R²⁹ are independentlymethylene, ethylene, trimethylene, tetramethylene, —C(CH₃)₂—,—CH((CH₂)₁₋₄CH₃)—, or —CH₂-phenylene.
 16. The polymerized composition ofclaim 1, wherein R¹¹ and R²⁸ are independently C₂-C₃₀ alkynyl having atleast two carbon-carbon triple bonds.
 17. The polymerized composition ofclaim 16, wherein R¹¹ and R²⁸ are independently—(CH₂)₈—C≡C—C≡C—(CH₂)₉CH₃, or —(CH₂)₈—C≡C—C≡C—(CH₂)₁₁CH₃.
 18. Thepolymerized composition of claim 1, wherein R¹³ is C₁-C₄ alkyl.
 19. Thepolymerized composition of claim 1, wherein R¹⁴ is C₁-C₄ alkylene. 20.The polymerized composition of claim 1, wherein R¹⁷ is2,5-dioxo-1-pyrrolidinyl.
 21. (canceled)
 22. The polymerized compositionof claim 1, wherein n is 3-17, 6-14, or 9-11.
 23. (canceled)
 24. Thepolymerized composition of claim 1, wherein the composition has a colorin the visible spectrum less than 570 nm.
 25. The polymerizedcomposition of claim 1, wherein the composition has a color in thevisible spectrum between 570 nm and 600 nm.
 26. The polymerizedcomposition of claim 1, wherein the composition has an observed color inthe visible spectrum greater than 600 nm. 27-30. (canceled)
 31. Apolymerized composition comprising the polymerization reaction productof at least one compound of the formula

wherein R¹ is

R² is C₇-C₂₀ alkylamino, or R³, R⁸ and R¹³, are independently C₁-C₂₀alkyl; R⁴, R⁷, R¹⁴, R¹⁶, R¹⁹ and R²⁰, are independently C₁-C₁₄ alkylene;R⁶, R¹⁵, and R¹⁸ are independently C₁-C₁₄ alkylene, or C₂-C₈ alkenylene,or C₆-C₁₃ arylene; R⁹ is C₁-C₁₄ alkylene; R¹⁰ and R¹², are independentlyC₁-C₁₄ alkylene or (C₁-C₁₄ alkylene) —(C₂-C₈ arylene); R¹¹ isindependently C₂-C₃₀ alkynyl; R¹⁷ is an ester activating group; R²¹ isC₁-C₂₀ alkylamino or C₁-C₂₀ alkyl; p is 1-5; n is 1-20; and wherein R¹and R² are not the same.
 32. The polymerized composition of claim 31,wherein R² is (C₇-C₁₈ alkyl)-NR³⁵ ₃X, wherein R³⁵ is H and each X isindependently F⁻, Br⁻, Cl⁻, I⁻, OH⁻, N₃ ⁻, HCO₃ ⁻, or CN⁻. 33.(canceled)
 34. The polymerized composition of claim 31, wherein R²¹ is(C₁-C₁₈ alkyl)-NR³⁵ ₃X, wherein R³⁵ is H or C₁-C₄ alkyl and each X isindependently F⁻, Br⁻, Cl⁻, OH⁻, N₃ ⁻, HCO₃ ⁻, or CN⁻.
 35. Thepolymerized composition of claim 31, wherein R² is (C₁-C₁₈ alkyl)-NR³⁵₃X, wherein R³⁵ is C₁-C₄ alkyl and each X is independently F⁻, Br⁻, Cl⁻,OH⁻, N₃ ⁻, HCO₃ ⁻, or CN⁻.
 36. The polymerized composition of claim 31,wherein R²¹ is decyl, undecyl, tridecyl, tetradecyl, pentadecyl,heptadecyl, —(CH₂)₁₀—NH₃X, —(CH₂)₁₀—N(CH₃)₃X, —(CH₂)₁₄—N(CH₃)₃X, or—(CH₂)₁₄—NH₃X, wherein each X is independently Cl⁻ or I⁻. 37-41.(canceled)
 42. A method for the detection of thermal radiationcomprising contacting a polymerized composition with thermal radiationand observing a color change, wherein the polymerized compositioncomprises the reaction product of at least one compound of the formula

wherein R¹ is

R² is

R³, R⁸, R¹³, R²⁴, R³¹ and R³³ are independently C₁-C₂₀ alkyl; R⁴, R⁵,R⁷, R¹⁴, R¹⁶, R¹⁹, R²⁰, R²², R²⁵, and R³² are independently C₁-C₁₄alkylene; R⁶, R¹⁵, R¹⁸, and R²⁶ are independently C₁-C₁₄ alkylene, C₂-C₈alkenylene, or C₆-C₁₃ arylene; R⁹ is C₁-C₁₄ alkylene or —NR³⁴—; R¹⁰,R¹², R²⁷, and R²⁹ are independently C₁-C₁₄ alkylene or (C₁-C₁₄alkylene)-(C₂-C₈ arylene); R¹¹ and R²⁸ are independently C₂-C₃₀ alkynyl;R¹⁷ is an ester activating group; R²¹ is C₁-C₂₀ alkylamino or C₁-C₂₀alkyl; R²³ is C₆-C₁₃ arylene; R³⁰ is C₁-C₁₄ alkylene or —NR³⁶—; R³⁴, andR³⁶ are independently H or C₁-C₄ alkyl;

R² is

R³, R⁸, R¹³, R²⁴, R³¹ and R³³ are independently C₁-C₂₀ alkyl; R⁴, R⁵,R⁷, R¹⁴, R¹⁶, R¹⁹, R²⁰, R²², R²⁵, and R³² are independently C₁-C₁₄alkylene; R⁶, R¹⁵, R¹⁸, and R²⁶ are independently C₁-C₁₄ alkylene, C₂-C₈alkenylene, or C₆-C₁₃ arylene; p is 1-5; n is 1-20; and wherein R¹ andR² are not the same.
 43. A method for the detection of electromagneticradiation in the ultraviolet range of the electromagnetic spectrumcomprising contacting at least one compound with electromagneticradiation in the ultraviolet range of the electromagnetic spectrum andobserving a color change, wherein the compound is of the formula

wherein R¹ is R⁹ is C₁-C₁₄ alkylene or —NR³⁴—; R¹⁰, R¹², R²⁷, and R²⁹are independently C₁-C₁₄ alkylene or (C₁-C₁₄ alkylene)-(C₂-C₈ arylene);R¹¹ and R²⁸ are independently C₂-C₃₀ alkynyl; R¹⁷ is an ester activatinggroup; R²¹ is C₁-C₂₀ alkylamino or C₁-C₂₀ alkyl; R²³ is C₆-C₁₃ arylene;R³⁰ is C₁-C₁₄ alkylene or —NR³⁶—; R³⁴, and R³⁶ are independently H orC₁-C₄ alkyl; p is 1-5; n is 1-20; and wherein R¹ and R² are not thesame.